Radiation diffraction colorants

ABSTRACT

A radiation diffraction material comprising an ordered periodic array of particles held in a polymeric matrix is disclosed; the particles each comprise a core surrounded by a shell of a non-film forming composition that is different from the matrix. Methods for using the material are also disclosed.

CROSS REFERENCE TO RELATED APPLICATION

The present application is a continuation of U.S. patent applicationSer. No. 11/263,679, filed Nov. 1, 2005, entitled “Radiation DiffractionColorants”, the entire disclosure of which is herein incorporated byreference.

FIELD OF THE INVENTION

This invention relates to Bragg diffracting colorants produced fromcore-shell particles.

BACKGROUND OF THE INVENTION

Goniochromaticity is the effect of perceived color varying as the angleof illumination or observation varies. Goniochromatic pigments are used,for example, in automotive coatings, decorative coatings, plasticpigmentation, printing inks (security inks in particular), textiles andcosmetics. Their optical effect results from the directional reflectionof light from predominantly sheet-like particles that conventionally aremetallic or that have a structured refractive index contrast, the lengthscale of which is comparable to the wavelength of light. According tothe nature of the pigment particles, the pigments are known as metalliceffect pigments (for example, aluminum, zinc, copper or alloys thereof)or interference pigments (for example, based on titanium dioxide-coatedmica, such as muscovite, phlogopite and biotite).

As a result of the incident light being reflected directionally by thepredominantly sheet-like particles, color effect pigments that areoriented, for example, in a coating, exhibit goniochromaticity; that is,their perceived color (lightness and/or hue and/or chroma) varies withthe angle of illumination or observation.

There is a need for durable goniochromatic materials that can beproduced in particulate form and that are suitable for use as colorantswith minimal haze.

SUMMARY OF THE INVENTION

The present invention is directed to a radiation diffraction materialcomprising an ordered periodic array of particles held in a polymericmatrix wherein said particles each comprise a core surrounded by a shellof a non-film forming composition that is different from said matrix.

The present invention is further directed to a method of producing aradiation diffractive material comprising the steps of:

-   -   applying a dispersion of core-shell particles onto a substrate,        the cores being substantially non-swellable and the shells being        non-film forming;    -   arranging the particles in an ordered periodic array that        diffracts radiation;    -   coating the array of particles with a matrix composition;    -   swelling the shells by diffusing components of the matrix into        the shells; and    -   fixing the coated array of particles.

The present method is further directed to a system for producingradiation diffractive material comprising:

-   -   a substrate for receiving a dispersion of core-shell particles        that form an ordered periodic array, the shells being swellable        and substantially non-film-forming;    -   a matrix delivery device for coating the array with a matrix        composition;    -   a radiation source for illuminating the coated array;    -   a radiation detector for measuring the spectrum of radiation        diffracted by the coated array; and    -   a curing system for curing components in the coated array and        fixing the relative positions of the particles.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-section of radiation diffractive material made inaccordance with the present invention;

FIG. 2 is a detailed view of the radiation diffractive material of FIG.1 showing Bragg diffraction of visible light at one viewing angle; and

FIG. 3 is a schematic of a process for preparing the radiationdiffractive material of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides radiation diffractive materialscomprising an ordered periodic array of core-shell particles fixedwithin a matrix with the shell material being non-film forming anddifferent from the matrix material. The materials are suitable for usein particulate form as colorants, among other things. As used herein,the term “colorants” refers to radiation diffractive materials thatdiffract radiation in the visible spectrum, while radiation diffractivematerial refers to material that diffracts any wavelength ofelectromagnetic radiation.

In certain embodiments, the core material and the shell material mayhave different indices of refraction. In addition, the refractive indexof the shell may vary as a function of the shell thickness as a gradientof refractive index through the shell thickness. The refractive indexgradient is a result of a gradient in the composition of the shellmaterial through the shell thickness.

In one embodiment of the invention, the gradient through the shellthickness of composition and properties is produced by applying adispersion of polymerizable core-shell particles onto a substrate, thecores being substantially non-swellable and the shells being non-filmforming. The particles are arranged into an ordered periodic array thatdiffracts radiation, and the array of particles is coated with a matrixcomposition. One or more components of the matrix diffuse into theshells resulting in gradients of the shell composition and of theproperties of the shell. The matrix composition may includecrosslinkable monomers. Polymerization of the matrix monomers in theshell and in the matrix fixes the array.

The present invention includes a system for producing radiationdiffractive material having a substrate for receiving a dispersion ofparticles that form an ordered periodic array and a matrix deliverydevice for coating the array with a matrix composition. A radiationsource is arranged to illuminate the coated array while a radiationdetector measures the spectrum of radiation diffracted by the coatedarray. The spacing between the particles is adjusted to achieve adesired wavelength of diffracted radiation. A curing system curescomponents in the coated array and fixes the relative positions of theparticles.

Referring to FIGS. 1 and 2, the radiation diffraction material 2 of thepresent invention includes an ordered periodic array of particles 4 heldin a polymeric matrix 6. The particles 4 are composed of a core 8surrounded by a shell 10. The material of the shell 10 is non-filmforming and is different from the material of the matrix 6. As such, thearray includes at least three general regions, namely, the matrix 6, theparticle shell 10 and the particle core 8. Typically, the particles 4are generally spherical with the diameter of the core 8 constituting 80to 90 percent of the total particle diameter or 85 percent of the totalparticle diameter with the shell 10 constituting the balance of theparticle diameter and having a radial thickness dimension. The corematerial and the shell material have different indices of refraction. Inaddition, the refractive index of the shell varies as a function of theshell thickness in the form of a gradient of refractive index throughthe shell thickness. The refractive index gradient is a result of agradient in the composition of the shell material through the shellthickness.

The matrix material is an organic polymer such as a polystyrene, apolyurethane, an acrylic polymer, an alkyd polymer, a polyester, asiloxane-containing polymer, a polysulfide, an epoxy-containing polymer,or a polymer derived from an epoxy-containing polymer. The material ofthe particle cores is also polymeric and may be chosen from the samepolymers as the matrix material and may also be inorganic material suchas a metal oxide (e.g., alumina, silica or titanium dioxide) or asemiconductor (e.g., cadmium selenide). The polymer(s) of the particleshells may be selected from the same list of polymers as the matrixmaterial; however, for a particular array of particles, the polymer(s)of the particle shell differ from the polymer(s) of the matrix material.By “non-film forming”, it is meant that the shell material remains inposition surrounding each particle core without forming a film of theshell material; as such, the core-shell particles are discrete particleswithin the matrix material. Such core-shell particles may be produced byemulsion polymerization of core monomers followed by polymerization ofshell monomers thereover.

The resultant core-shell particles are arranged into an ordered array bydispersing the core-shell particles in a carrier and coating thedispersion onto a substrate. The dispersion of the particles may contain1 to 70 vol. % of the particles, or 30 to 65 vol. % of the particles. Asuitable composition for the carrier is water. The dispersion may becoated onto a substrate by various techniques including dipping,spraying, brushing, roll coating, gravure coating, curtain coating, flowcoating, slot-die coating, or ink-jet coating. The particles in thedispersion are all similarly charged, which causes them to repel eachother and form a periodic array of particles. The substrate coated witha layer of the dispersion is dried to remove the carrier from thedispersion so that the particles pack substantially adjacent to eachother in three dimensions. The drying may be achieved using forced air,or by convective or radiative heating of the substrate and/or thedispersion.

A precursor matrix material (containing monomers) is applied to thepacked particles on the substrate by any suitable technique such asspraying, brushing, roll coating, gravure coating, curtain coating, flowcoating, slot-die coating, or ink-jet coating and interpenetrates thearray with a fluid matrix composition. The monomers of the matrixcomposition flow around the core-shell particles and fill into theinterstitial spaces between the particles in the packed array. Some ofthe matrix monomer(s) diffuse into the shells of the particles, therebyswelling the shells and increasing the shell thickness. The matrixmonomers diffuse into the shells as a gradient through the thickness ofthe shells with the highest concentration of matrix monomers being atthe outer edge of the shell and the lowest concentration of matrixmonomers being adjacent the interface between the shell and the core.

The matrix composition is cured (such as by exposure to ultra-violetlight) to polymerize the matrix material in the interstices of the arrayand the matrix material that diffused into the particle shells therebyfixing the dimension of the shells and the position of the particleswithin the matrix polymer. Other curing mechanisms may be used to fixthe matrix composition within and around the particles. The matrixmonomers diffused into the shells polymerize within the shells creatinga gradient of matrix polymer in the shell with the highest concentrationof matrix polymer being at the outer edge of the shell adjacent thematrix and the lowest concentration of matrix polymer being adjacent theinterface between the shell and the core.

Referring to FIG. 2, the array of particles 2 diffract radiationaccording to Bragg's law. Incident radiation (ray I) is partiallyreflected (ray R₁) at the uppermost layer of particles in the array atan angle θ to the plane of the first layer and is partially transmitted(ray T) to underlying layers of particles. Some absorption of incidentradiation occurs as well. The portion of transmitted radiation is thenitself partially reflected (ray R₂) at the second layer of particles inthe array at the angle θ (with some absorption) and partiallytransmitted to underlying layers of particles. This feature of partialreflection at the angle θ and partial transmission to underlying layersof particles continues through the thickness of the array. Thewavelength of the reflected radiation satisfies the equation:

mλ=2nd sin θ

where (m) is an integer, (n) is the effective refractive index of thearray and (d) is the distance between the layers of particles. Theeffective refractive index (n) is closely approximated as a volumeaverage of the refractive index of the materials of the particles. Forgenerally spherical particles, the dimension (d) is the distance betweenthe plane of the centers of particles in each layer and is proportionalto the particle diameter. In such a case, the reflected wavelength λ isalso proportional to the particle diameter.

The present invention further includes a system for producing radiationdiffractive material. In one embodiment shown in FIG. 3, a dispersion 22of particles 4 in a carrier is coated onto a substrate 24. FIG. 3depicts the substrate 24 traveling in the direction of arrow A and beingdipped into a vessel containing the dispersion 22 to coat the dispersion22 onto the substrate 24, but this method of applying the dispersion 22to the substrate 24 is not meant to be limiting and may include themethods described above. The particles 4 form into a periodic array andthe carrier is removed from the dispersion at 26 (such as byevaporation) to yield essentially only a periodic array of particles 4remaining on the substrate 24. The array of particles is interpenetratedwith a fluid matrix monomer composition at 28. Some of the monomercomposition diffuses into the shells, thereby increasing the shellthickness (and particle diameter) until the matrix composition is curedat 30. The length of time between application of the monomers onto thearray and curing at 30 in part determines the degree of swelling by theshells.

The wavelength and intensity of the reflected light can be selected byvarying the spacing (d) between the layers (by adjusting the size of theparticles), the quantity of particle layers, the difference in therefractive index between the polymeric matrix and the particles, and theeffective refractive index (n) of the radiation diffractive materialaccording to Table 1.

TABLE 1 Variable Increased Decreased (with other variables constant)variable variable Spacing between layers (d) Longer λ Shorter λ Numberof layers Higher intensity Lower intensity Difference in refractiveindex Higher intensity Lower intensity between particles and matrixDegree of change in refractive index More scattering Less scatteringbetween matrix and particles and haze and haze Effective refractiveindex (n) Longer λ Shorter λ

The distance (d) between layers of particles in the array may be alteredto shift the wavelength of diffracted radiation, i.e., increase theinterparticle distance (d) to increase the wavelength or decrease theinterparticle distance (d) to decrease the wavelength. It will beappreciated that the particle size of preformed particles having a fixeddimension is not readily adjusted in a continuous operation. Therefore,in one embodiment of the invention, when a change in particle size isnecessary to adjust the diffraction wavelength, particles having alarger diameter may be used to prepare the array. This requires that theprocess be changed over to operation with different particles that maynot allow for continuous preparation of array on the substrate. However,the core-shell particles of the present invention are particularlysuited for on-line adjustment of particle size. The particle size is inpart determined by the degree of swelling in the shell, i.e., the amountof matrix monomers that are allowed to diffuse into the shell prior tocuring.

The periodic array of particles exhibits Bragg diffraction of radiationthat may be monitored and controlled via an illuminating radiationsource 32, a detector of diffracted radiation 34, including aspectrograph 36 (displaying absorbance as a function of wavelength) anda control system 38 for adjusting the wavelength of diffractedradiation. The illuminating radiation source 32 may include a lightemitting diode (LED) and optical fibers for transporting illuminatinglight from the LED to the array and reflected light from the array backto the detector 34. The wavelength of illuminating radiation may be inthe visible or non-visible spectrum. Radiation diffracted by the arrayand reflected back from the array is received by the detector and may bedisplayed on spectrograph 36. The system 20 includes a control system 38(such as a computer with software) for correlating the measured spectrumof diffracted light with a desired appearance and for altering thewavelength of diffracted radiation. The control system 38 determines thelength of time that the matrix monomers are allowed to diffuse into theparticle shells. If the control system 38 determines that the wavelengthof diffracted radiation is shorter than desired, the control system 38increases the time before curing to allow more monomers to diffuse intothe particle shells thereby increasing the particle diameter andincreasing the interparticle distance (d). For example, the rate oftravel of the substrate 24 may be slowed to increase the time fordiffusion of matrix monomers into the particle shells before curing. Adesired colored appearance of the array 2 can be selected using thecomputer 38 to correlate the reflected spectrum at 36 with apparentcolor. For example, a desired shade of blue light reflected from thearray 2 has a signature spectrum of absorbance versus wavelength. Whenthe computer 38 determines that the absorbance spectrum sufficientlymatches the desired signature spectrum, the array 2 produced willexhibit the desired blue light. In this manner, production of the array2 can be controlled based on the absorbance spectrum. It will beappreciated that other types of components for the radiation source 32,the detector 34, spectrograph 36 and control system 38 are within thescope of the invention.

The radiation diffractive material may remain on the substrate as agoniochromatic film covering the substrate. Alternatively, the radiationdiffractive material may be removed from the substrate as a continuousfilm for application to a device such as by lamination using adhesivesor the like. In another embodiment of the invention (as shown in FIG.3), the radiation diffractive material is comminuted into particulateform (e.g., as flakes) for use as a colorant in a colored coatingcomposition when the reflected radiation is visible light. The coloredcoating composition may be a paint, ink, a cosmetic or other decorativecomposition.

The average particle size of the particles is about 0.01 to about 1micron or 0.06 to 0.5 micron. The distance (d) between the layers iscontrolled substantially by the size of the particles. If the particlesize varies within a layer or if the particle size varies betweenlayers, the spacing (d) between the layers will vary through the array.As noted above, the wavelength λ of light reflected under the Braggcondition is a function of the spacing (d) between the layers. Adistribution in particle size causes variation in the wavelength ofreflected light that is viewed as a broad bandwidth of light exhibitinga blend of colors instead of a clean, sharp color. Therefore, in orderto maintain a regular array, the particles are similarly sized and,preferably, differ in size from each other by a maximum of 15% or amaximum of 5 percent.

For use in typical automotive coatings and industrial coatings (e.g.,for cell phones) of conventional thickness, the radiation diffractivematerial may have a maximum thickness of 20 microns, such as 10 micronsor less or 5 microns or less, such as 2 microns. Materials substantiallythicker than 20 microns may be difficult to properly disperse and alignin a typical automotive or industrial coating. Materials substantiallythicker than 20 microns may also cause a roughening of the surface of atypical automotive or industrial coating, causing a reduction in thegloss of the coating, which may or may not be desirable. Thickermaterials may be acceptable or desirable in other types of coatings thatare thicker than automotive coatings, and may also be acceptable ordesirable, for example, in plastic pigmentation, textiles and cosmeticsand/or in applications wherein a “roughened” or reduced gloss appearanceis desired. The number of layers of particles in the radiationdiffractive material is selected to achieve the desired opticalproperties using the minimum number of layers for achieving the desiredintensity of color. At these dimensions, the radiation diffractivematerial has an aspect ratio that allows materials in a coatingcomposition to align with each other, and with the coated substrate,along their long axes. A suitable aspect ratio for the radiationdiffractive material in an automotive coating composition is at least 2,or 5 to 100, such as 10.

The interference effect (the intensity of the reflected radiation) maybe increased by increasing the number of layers in the array. While atleast two layers are needed to induce a Bragg effect on the incidentlight, at least five or at least ten layers of particles can achieve adesired intensity of reflected radiation. Fewer layers of particlesreflect less radiation thereby decreasing the intensity of the reflectedradiation and tending to broaden the wavelength of the reflectedradiation. More than about ten layers may be used in certainapplications where higher intensity reflected radiation is desired. Anincrease in the shell thickness (i.e., increase in particle size)increases the distance (d) between layers of particles in the array,thereby increasing the wavelength of diffracted radiation.

The interference effect is also increased by increasing the differencein refractive index between the particles and the surrounding matrix. Inconventional Bragg arrays of packed particles, the effective refractiveindex of the material in a plane through the centers of a layer ofparticles is close to the refractive index of the particles becauselittle or no matrix material is found in that plane. A plane takenthrough the edges of the particles passes through matrix material andmaterial of the particles. Hence, the effective refractive index throughthe plane of the particle edges is determined by both materials (matrixand conventional particle) and the difference in effective refractiveindex between the plane of the particle centers and a plane through theparticle edges is somewhat less than the difference in refractive indexbetween the particle material and the matrix material.

In contrast, the core-shell particles of the present invention providegreater difference in refractive index (and greater interference effect)than conventional particles due to the presence of the shell. Theeffective refractive index of the material 2 taken through a plane Cthrough the centers of the particles is based primarily on therefractive index of the core material. The effective refractive index ofthe material 2 taken through a plane S through the shells of theparticles is based on the refractive index of the shell material and thematrix material. In this manner, the difference in refractive indexbetween the plane C and the plane S is maximized and can be greater thanis achieved with conventional (not core-shell) particles.

In addition, while a greater difference in refractive index between theparticles and the surrounding matrix induces greater intensity ofreflected radiation, some scattering of incident radiation is typicallyassociated with a step change in refractive index such as can existbetween the matrix and particles of conventional Bragg arrays. Scatteredincident radiation reduces the intensity of reflected radiation in thedesired wavelength and broadens the spectrum of reflected radiation. ForBragg diffraction of light, the reflected color appears hazy. Thisundesired phenomenon of scattered radiation is minimized in the presentinvention where the change in refractive index of the radiationrefractive material is less dramatic. The refractive index of theradiation refractive material shifts from the refractive index of thematrix polymer to a gradient of refractive index through the thicknessof the shell corresponding to the gradient of concentration of matrixpolymer through the shell thickness.

The present invention is not limited to use in diffracting visiblelight. Other wavelengths of electromagnetic radiation outside thevisible spectrum may be reflected, such as ultraviolet radiation orinfrared radiation. The ordered array in the matrix may be used toreflect such radiation to prevent or minimize exposure of a substrate onwhich the array is positioned to that radiation. The wavelength λ of thereflected radiation may be selected as described above by adjusting theeffective refractive index (n) and the distance (d) between the layers.

The refractive index of the matrix composition also may be adjusted toalter the difference between the refractive index of the particles andthe refractive index of the matrix by adding nanoscale particles (sized1 to 50 nm) to the matrix. The nanoscale particles have particle sizesless than the wavelength of visible light and, thus, do notsubstantially reflect or scatter light. Suitable materials for thenanoscale particles that increase the effective refractive index of thematrix include metals (for example, gold, silver, platinum, copper,titanium, zinc, nickel), metal oxides (for example, aluminum oxide,cerium oxide, zinc oxide, titanium dioxide), mixed metal oxides, metalbromides and semiconductors. Suitable materials for the nanoscaleparticles that decrease the effective refractive index of the matrixinclude metal oxides (for example, silica), mixed metal oxides and metalfluorides (for example, magnesium fluoride, calcium fluoride). Nanoscaleair bubbles may also be produced in the polymer matrix to decreaserefractive index of the matrix. Similarly, the refractive index of theparticles may be adjusted by adding nanoscale particles to theparticles.

In another embodiment of the present invention, a coating compositionhaving a perceived color that exhibits goniochromaticity, that is, theperceived color varies with angle of illumination or observation, isproduced. The goniochromatic coating composition includes one or morefilm forming materials (discussed below) and a plurality of theradiation diffracting material of the present invention functioning ascolorants and, if desired, other additives described below. Infunctioning as colorants, the radiation diffracting material diffractsvisible light.

The type and amount of film-forming material and other componentsincluded in the coating composition will depend in part upon the natureof the coating and its method of application. No particular measureshave been found necessary to incorporate the colorants of the presentinvention into typical coating formulations. If desired, for the sake ofimproved dispensability, the colorants can first be incorporated into apolymeric vehicle in the form of a paste, optionally aided by theaddition of surfactants conventionally used with other types ofpigments.

The specific colorant to film-forming component ratio can vary widely solong as it provides the requisite color appearance at the desired filmthickness and application solids and will depend upon the particularingredients employed, the type of surface to be coated, the intended useof the surface, as well as such factors as the specific size of thecolorants used. On a volume basis, the amount of colorant would usuallybe similar to that employed with other color effect pigments, such ascoated micas or natural pearlescence (fishsilver). Although there are nocritical limits, the effects may not be perceptible in most applicationsat colorant concentrations less than 0.2 volume percent, and it would beunusual for a coating to contain more than 50 volume percent of thesespecial effect colorants (the percentages based on total solids contentof the coating composition).

The special effect colorants of the present invention can be used in awide variety of coating compositions, such as paints, inks, nail polish,and other cosmetics. These include waterborne and solvent-borne liquidcoating compositions, powder coating compositions, powder slurrycompositions and electrodeposition compositions. They can be used inclear coatings (i.e., those that produce cured films having substantialtransparency) or they can be added to other pigments and/or dyes incolored coatings. Functionally, the coatings that may include thecolorants of the present invention include primers, basecoats andtopcoats, as well as any one or more of the coatings in a multi-coatcombination. Compatibility of the colorants with a variety of polymertypes has been observed, and it can be expected that any knownfilm-forming polymer composition used for coatings could be used. Someof the more common families of polymer compositions used in coatingsinclude polyurethanes, acrylic polymers, alkyd polymers, polyesters,siloxane-containing polymers, polysulfides, epoxy-containing polymersand polymers derived from epoxy-containing polymers and combinationsthereof. These are known to be provided in coatings as lacquers,thermoplastics or thermosetting types of compositions. Thermosettingcompositions will further include crosslinking agents, such aspolyisocyanates, amino-formaldehyde aminoplasts, polyacids,polyanhydrides and combinations thereof. As used herein, “film-forming”means that the film-forming materials form a self-supporting continuousfilm on at least a horizontal surface upon removal of any solvents orcarriers present in the composition or upon curing at ambient orelevated temperature. Inks refer to compositions that are suited for usein conventional printing processes.

Volatile materials that can be included as diluents in the liquid orpowder slurry coating compositions include water and/or organicsolvents, such as alcohols, ethers and ether alcohols, ketones, esters,aliphatic and alicyclic hydrocarbons and aromatic hydrocarbons as arecommonly employed in the coating industry. Examples of solvents forcoatings include aliphatic solvents, such as hexane, naphtha and mineralspirits; aromatic and/or alkylated aromatic solvents, such as toluene,xylene and SOLVESSO 100 (aromatic blend from Exxon Chemicals); alcohols,such as ethyl, methyl, n-propyl, isopropyl, n-butyl, isobutyl and amylalcohol, and m-pryol; esters, such as ethyl acetate, n-butyl acetate,isobutyl acetate and isobutyl isobutyrate; ketones, such as acetone,methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, methyln-amyl ketone, and isophorone, glycol ethers and glycol ether esters,such as ethylene glycol monobutyl ether, diethylene glycol monobutylether, ethylene glycol monohexyl ether, propylene glycol monomethylether, propylene glycol monopropyl ether, ethylene glycol monobutylether acetate, propylene glycol monomethyl ether acetate, anddipropylene glycol monomethyl ether acetate.

The coating compositions can further include one or more additives, suchas UV absorbers and stabilizers, rheology control agents, surfactants,catalysts, film build additives, fillers, flatting agents, deformers,microgels, pH control additives and other pigments. Along with thecolorants of the present invention, it may be useful in some cases toalso include conventional pigments and dyes. These include micas, ironoxides, carbon black, titanium dioxide, aluminum flakes, bronze flakes,coated mica, nickel flakes, tin flakes, silver flakes, copper flakes andcombinations thereof. Other organic coloring agents (i.e., dyes ororganic pigments) could also be included. If it is desired to match thespecific gravity of the polymeric and solvent components of the coatingcomposition, the colorant content of the composition will haveessentially no elemental metal components, and, preferably, essentiallyno metal oxide components as well.

Coated finishes, particularly for automobiles, are often provided bymultiple layers of different coatings. An automobile coating maytypically include an electrodeposited primer, a primer-surface coat, acolored basecoat and a clear topcoat. Additional coating layers may beused for appearance or performance purposes. The colorants of thepresent invention can be incorporated in an otherwise clear coat that isapplied over a basecoat not containing the colorant but pigmentedconventionally (i.e., a so-called “color-plus-clear” composite finish).Either or both of the basecoat and clear coat in this example may bewaterborne as is known in the art.

In yet another alternative embodiment, the coating that includes thecolorant can be a basecoat, over which is applied a clearcoat that doesnot contain the colorant. The components of the basecoat and those ofthe clearcoat can be any of those discussed above.

In yet another alternative embodiment, the coating that includes thecolorant can be a clearcoat that is applied over a basecoat that alsocontains colorant. The components of the basecoat and those of theclearcoat can be any of those discussed above.

In yet another alternative embodiment, the coating that includes thecolorant can be a clearcoat that is applied over a basecoat that doesnot contain colorant, and over which is applied another clearcoat thatdoes not contain colorant. The components of the basecoat and those ofthe two clearcoats can be any of those discussed above.

The liquid or powder slurry coatings can be applied to the surface to becoated by any suitable coating process well-known to those skilled inthe art, for example by dip coating, direct roll coating, reverse rollcoating, curtain coating, spray coating, brush coating, gravure coating,flow coating, slot-die coating, ink-jet coating, electrodeposition andcombinations thereof. Powder coatings are generally applied byelectrostatic deposition.

The present invention also includes use of the radiation diffractivematerial in other types of carriers than a film-forming component. Theradiation diffractive material may be included as a component dispersedin a cosmetic or impregnated into plastic.

The preparation and use of radiation diffractive material of the presentinvention is illustrated in the examples that follow. The followingexamples are merely illustrative of the invention and are not intendedto be limiting. Unless otherwise indicated, all parts are by weight.

EXAMPLES Example 1 Organic Polymer Matrix

An ultraviolet radiation curable organic composition was prepared viathe following procedure. Diphenyl(2,4,6-trimethylbenzoyl)phosphineoxide/2-hydroxy-2-methyl-propiophenone (22.6 g), 50/50 blend fromAldrich Chemical Company, Inc., Milwaukee, Wis., in 615 g ethyl alcoholwere added with stirring to 549 g of propoxylated (3) glyceryltriacrylate, 105.3 g of pentaerythritol tetraacrylate and 97.8 g ofethoxylated (5) pentaerythritol tetraacrylate all from Sartomer Company,Inc., Exton, Pa., to produce a curable organic matrix composition.

Example 2 Organic Core-Shell Particles

A dispersion of polystyrene-divinylbenzene core/styrene-methylmethacrylate-ethylene glycol dimethacrylate-divinylbenzene shellparticles in water was prepared via the following procedure. 4.9 gramsof sodium bicarbonate from Aldrich Chemical Company was mixed with 4090g deionized water and added to a 12-liter flask equipped with athermocouple, heating mantle, stirrer, reflux condenser and nitrogeninlet. The mixture was sparged with nitrogen for 40 minutes withstirring and then blanketed with nitrogen. Surfactant Aerosol MA80-I(46.0 g in 410 g deionized water) from Cytec Industries, Inc., was addedto the mixture with stirring followed by a 48 g deionized water rinse.The mixture was heated to approximately 50° C. using a heating mantle.Styrene monomer (832.8 g), available from Aldrich Chemical Company,Inc., was added with stirring. The mixture was heated to 60° C. Sodiumpersulfate from Aldrich Chemical Company, Inc. (12.5 g in 144 gdeionized water) was added to the mixture with stirring. The temperatureof the mixture was held constant for 40 minutes. Under agitation, 205.4g of divinylbenzene from Aldrich Chemical Company, Inc., was added tothe mixture and the temperature was held at approximately 60° C. for2.25 hours. Sodium persulfate from the Aldrich Chemical Company, Inc.(9.1 g in 86.4 g deionized water) was added to the mixture withstirring. A mixture of styrene (200 g), methyl methacrylate (478.8 g),ethylene glycol dimethacrylate (48 g) and divinylbenzene (30.2 g) allavailable from Aldrich Chemical Company, Inc., was added to the reactionmixture with stirring. Surfactant Sipomer COPS-I(3-allyloxy-2-hydroxy-1-propanesulfonic acid 82.7 g) from Rhodia, Inc.,Cranbury, N.J., was added to the reaction mixture with stirring. Thetemperature of the mixture was maintained at 60° C. for four hours. Theresulting polymer dispersion was filtered through a five-micron filterbag. The polymer dispersion was then ultrafiltered using a 4-inchultrafiltration housing with a 2.41-inch polyvinylidine fluoridemembrane, both from PTI Advanced Filtration, Inc., Oxnard, Calif., andwas pumped using a peristaltic pump at a flow rate of approximately 170ml per second. Deionized water (3000 g) was added to the dispersionafter 3000 g of ultrafiltrate had been removed. This exchange wasrepeated several times until 10023 g of ultrafiltrate was replaced with10037 g of deionized water. Additional ultrafiltrate was then removeduntil the solids content of the mixture was 45 percent by weight.

Example 3 Particles on Substrate

The material prepared in Example 2 (1575 grams) was applied via aslot-die coater from Frontier industrial Technology, Inc., Towanda, Pa.to a polyethylene terephthalate substrate and dried at 180° F. for 30seconds to a porous dry thickness of approximately 3.5 microns. Theresulting deposited particles diffracted light at 541 nm when measuredwith a Cary 500 spectrophoto-meter from Varian, Inc. The particles wereloosely deposited on the polyethylene terephthalate substrate and couldeasily be wiped off when touched lightly.

Examples 4-5 Backfilling of Particles

The curable organic matrix composition prepared in Example 1 (1389grams) was applied into the interstitial spaces of the porous driedparticles on the polyethylene terephthalate substrate prepared inExample 3 using a slot-die coater from Frontier Industrial Technology,Inc. After application, the samples were dried in an oven at 120° F. fora length of time listed in Table 1 and then ultraviolet radiation curedusing a 100 W mercury lamp. The resulting flexible, transparent filmsviewed at 0 degrees or parallel to the observer had a red color. Thesame films, when viewed at 45 degrees or greater to the observer, wereorange-green in color. The films were measured using a Cary 500spectrophotometer from Varian, Inc and diffracted light as listed inTable 2.

TABLE 2 Example Drying Time Wavelength 4 2 minutes 644 nm 5 1 minute 629 nm

Example 6 Flake Milling

The material prepared in Example 4 was washed two times with a 50/50mixture of deionized water and isopropyl alcohol. The material was thenremoved from the polyethylene terephthalate substrate using an air knifeassembly from the Exair Corporation, Cincinnati, Ohio. The material wascollected via vacuum into a collection bag. The loose material was thenground into powder using an ultra-centrifugal mill from Retsch GmbH &Co., Haan, Germany. The powder was then passed through a 38 micron and a25 micron stainless steel sieve from Fisher Scientific International,Inc. The material in the 25 micron sieve was collected as a powder.

Example 7 Coating Composition Containing Colorant with Core-ShellParticles

The powder from Example 6 was added to a container containing the firstcomponent of a film-forming binder and a diluent. The container wascapped and hand shaken for 1 minute. After shaking, the container wasreopened and a crosslinking agent was added. The container was resealedand hand shaken for one minute. The resulting coating composition havingthe composition as listed in Table 3 was ready for spray application.

TABLE 3 Component Wt. % Film-forming binder¹ 54.57 Diluent² 20.46Example 6 powder 6.82 Crosslinking agent³ 18.15 Total 100 ¹DCU2055, aclearcoat composition available from PPG Industries, Inc., Pittsburgh,PA. ²DT 870, a reducer available from PPG Industries, Inc. ³DCX61, acrosslinking agent available from PPG Industries, Inc.

A black coated steel panel (APR45583 available from ACT Laboratories,Inc., Hillsdale, Mich.) was scuff-sanded with a very fine Scotch-BritePad (abrasive pad available from the 3M Corp., Minneapolis, Minn.). Thesanded panel was hand wiped and cleaned with a degreaser (DX330,available from PPG Industries, Inc.). The panel was then spray coatedwith the coating composition containing the material from Example 6.

The coated panel was flashed for 10 minutes at ambient conditions andwas then baked at 140° F. for 30 minutes and was allowed to cure for 24hours. The panel was scuff sanded with very fine Scotch-Brite pads andwas cleaned with isopropanol. The panel was recoated with a protectiveclearcoat comprised of DCU2055 and DCX61.

The panel sat at ambient conditions for 10 minutes, was baked at 140° F.for 20 minutes, allowed to cure for 24 hours and was visually inspected.The coated panel at 0 degrees or parallel to the observer had a redcolor. The same coated panel, when viewed at 45 degrees or greater tothe observer, was orange-green in color.

Although the present invention has been described with reference tospecific details of certain embodiments thereof, it is not intended thatsuch details should be regarded as limitations upon the scope of theinvention except insofar as they are included in the accompanyingclaims.

As used herein, unless otherwise expressly specified, all numbers suchas those expressing values, ranges, amounts or percentages may be readas if prefaced by the word “about”, even if the term does not expresslyappear. Any numerical range recited herein is intended to include allsub-ranges subsumed therein. Plural encompasses singular and vice versa.Also, as used herein, the term “polymer” is meant to refer toprepolymers, oligomers and both homopolymers and copolymers; the prefix“poly” refers to two or more.

1. A radiation diffractive material, comprising: an ordered periodicarray of particles packed adjacent to each other, said array defininginterstitial spaces between adjacent particles, said particles eachcomprising a core surrounded by a non-film forming shell; and a matrixcomposition interpenetrated into the interstitial spaces in the arrayand cured therein.
 2. The radiation diffraction material of claim 1,wherein the refractive index of said core is different from therefractive index of said shell.
 3. The radiation diffraction material ofclaim 2, wherein said shell has a gradient of refractive index acrossthe thickness of said shell.
 4. The radiation diffraction material ofclaim 1, wherein said matrix and said shell each comprise a polymericmaterial different from each other, wherein the polymeric materialcomprises a polystyrene, a polyurethane, an acrylic polymer, an alkydpolymer, a polyester, a siloxane-containing polymer, a polysulfide, anepoxy-containing polymer and/or a polymer derived from anepoxy-containing polymer.
 5. The radiation diffraction material of claim4, wherein said shell is swellable by monomers of said matrix polymerand said core is substantially non-swellable.
 6. The radiationdiffraction material of claim 2, wherein said particle core comprises apolymeric material comprising a polystyrene, a polyurethane, an acrylicpolymer, an alkyd polymer, a polyester, a siloxane-containing polymer, apolysulfide, an epoxy-containing polymer, a polymer derived from anepoxy-containing polymer, a metal oxide and/or an inorganic polymer. 7.The radiation diffraction material of claim 1, wherein the diameter ofsaid core is 80 to 90 percent of the total particle diameter.
 8. Theradiation diffraction material of claim 1, wherein the radiationdiffraction material is in the form of a sheet.
 9. The radiationdiffraction material of claim 1, wherein the radiation diffractionmaterial is in particulate form.
 10. A method of producing a radiationdiffractive material comprising: applying a dispersion of particles ontoa substrate, the particles each comprising a core surrounded by anon-film forming shell; packing the particles adjacent to each other inan ordered periodic array that diffracts radiation, such that the arraydefines interstitial spaces between adjacent particles; filling theinterstitial spaces in the array of particles with a curable matrixcomposition; swelling the shells by diffusing components of the matrixcomposition into the shells; and curing the matrix composition.
 11. Themethod of claim 10, wherein the diffusing components comprisescrosslinkable monomers.
 12. The method of claim 10, wherein thediffusing components comprises solvent.
 13. The method of claim 10,wherein said swelling step produces a gradient of refractive indexthrough the thickness of the shell.
 14. The method of claim 10, whereinsaid swelling step further comprises identifying the diffractionwavelength of the array and adjusting the degree of swelling of theshells to achieve a desired diffraction wavelength of the array.
 15. Themethod of claim 10, further comprising removing the radiationdiffractive material from the substrate.